Carbamic acid esters and use as pesticides

ABSTRACT

Carbamic acid compounds of the formula ##STR1## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X and Y are as hereinafter set forth, processes for their preparation, pesticidal compositions containing one or more of the carbamic acid compounds as the active ingredient and methods for using the pesticidal compositions for the control of pests, particularly insects, mites and nematodes, are described.

DETAILED DESCRIPTION OF THE INVENTION

The invention is directed to carbamic acid derivatives of the generalformula ##STR2## wherein R¹ is hydrogen, halogen, methyl, ethyl,trifluoromethyl or nitro; R² is hydrogen, halogen, methyl ortrifluoromethyl; R³ is hydrogen, halogen or methyl; R⁴ is hydrogen ormethyl; R⁵ is hydrogen or C₁₋₄ -alkyl, whereby both symbols R⁴ and R⁵are not simultaneously hydrogen; R⁶ is C₁₋₄ -alkyl; X is oxygen,methylene or carbonyl; and Y is oxygen or sulfur.

This invention is also directed to compositions effective for pestcontrol and especially for the control of insects, mites and nematodes,which contain, as the active component, one or more compounds of formulaI. Finally, this invention is directed to processes for the preparationof such compositions.

As used herein, the term "halogen" denotes fluorine, chlorine, bromineand iodine. The term "C₁₋₄ -alkyl" denotes not only straight-chain butalso branched-chain alkyl groups such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl and tert.butyl.

Since the compounds of formula I can contain asymmetric carbon atoms,these compounds can exist as optical antipodes. Formula I is accordinglyintended to include these possible isomeric forms as well as theracemates.

If R¹ or R³ is halogen, this is preferably fluorine, chlorine orbromine. If R² is halogen, then this is preferably fluorine or chlorine.

If R⁵ is C₁₋₄ -alkyl, then this is preferably methyl or ethyl.

R¹ preferably is hydrogen, halogen, methyl or trifluoromethyl.

R² preferably is hydrogen or halogen.

R³ preferably is hydrogen.

R⁵ preferably is hydrogen, methyl or ethyl.

R⁶ preferably is methyl, ethyl, isopropyl or isobutyl.

X preferably is oxygen or methylene.

Preferred compounds of formula I are:

Ethyl [2-(p-phenoxyphenoxy)ethyl]ethylcarbamate,

ethyl 2-(p-phenoxyphenoxy)propylcarbamate,

ethyl [2-(p-phenoxy-m-tolyloxy)ethyl]methylcarbamate,

methyl [2-(p-phenoxyphenoxy)ethyl]methylcarbamate,

isopropyl [2-(p-phenoxyphenoxy)ethyl]methylcarbamate,

S-ethyl [2-(p-phenoxyphenoxy)ethyl]methylthiocarbamate,

ethyl {2-[p-(m-chlorophenoxy)phenoxy]ethyl}methylcarbamate,

ethyl {2-[p-(m-bromophenoxy)phenoxy]ethyl}methylcarbamate,

ethyl 2-(p-benzylphenoxy)propylcarbamate,

ethyl 2-[p-(m-fluorophenoxy)phenoxy]propylcarbamate, and

ethyl {2-[p-(m-fluorophenoxy)phenoxy]ethyl}methylcarbamate.

Especially preferred compounds of formula I are:

ethyl {2-[p-(p-fluorophenoxy)phenoxy]ethyl}methylcarbamate,

ethyl [2-(p-phenoxyphenoxy)ethyl]methylcarbamate,

ethyl {2-[p-(3,5-dichlorophenoxy)phenoxy]ethyl}methylcarbamate, and

ethyl 2-[p-(p-fluorophenoxy)phenoxy]propylcarbamate.

The compounds of formula I of this invention are prepared by theprocesses described below.

Procedure A

Reacting a phenol of the formula ##STR3## wherein R¹, R², R³ and X areas defined hereinabove, with a compound of the formula ##STR4## whereinR⁴, R⁵, R⁶ and Y are as defined hereinabove and Q is a leaving group,especially chlorine, bromine, iodine, mesyloxy or tosyloxy.

A starting material of formula II is reacted with a compound of formulaIII conveniently in an inert organic solvent and in the presence of anacid-binding agent. Representative inert organic solvents includedimethylformamide, dioxan, hexamethylphosphoric acid triamide,tetrahydrofuran, dimethoxyethane, toluene and combinations of two ormore of these solvents. Preferred acid-binding agents are alkali metals,especially sodium and potassium, alkali metal hydrides, alkali metalamides, alkali metal hydroxides and alkali metal carbonates, especiallypotassium carbonate. In this case, the corresponding alkali metalphenolate is formed from the phenol of formula II. Alternatively, thephenolate is formed from the phenol in the presence of an alkali metalhydroxide by azeotropically removing the resulting water with toluene.

The reaction temperature can vary over a wide range. In general, thereaction is carried out at a temperature between -20° C. and the boilingpoint of the reaction mixture, preferably between room temperature and100° C., especially between 80° C. and 100° C. When the leaving group Qin formula III is bromine or iodine, the reaction temperatures arepreferably somewhat lower than those when a compound of formula III inwhich the leaving group Q is chlorine, mesyloxy or tosyloxy is used.

The isolation of compounds of formula I is carried out using standardprocedures.

Procedure B

Reacting an amine of the formula ##STR5## wherein R¹, R², R³, R⁴, R⁵ andX are as defined hereinabove, with a compound of the formula ##STR6##wherein R⁶ and Y are as defined hereinabove, conveniently in thepresence of an inert organic solvent and an acid-binding agent.

Representative inert organic solvents include acetone and methylenechloride. The reaction is preferably carried out in the presence of anacid-binding agent such as, for example, an alkali metal carbonate,preferably potassium carbonate. The reaction is preferably carried outat the reflux temperature of the reaction mixture. In general, thereaction is finished within one day. Thereafter, undissolved salts whichmay be present are conveniently filtered off from the reaction mixtureand the filtrate is evaporated in vacuo. The residue is purified, forexample by column chromatography, distillation or crystallization.

Insofar as no planned synthesis for the isolation of pure isomers iscarried out, a product is normally obtained as a mixture of two isomers.The isomers can be separated employing standard procedures.

The starting materials of formulae II, III, IV and V are known or can beprepared according to known methods.

The compounds of formula I of this invention are active as pesticidesand are especially valuable in the control of insects, mites andnematodes. They are especially valuable against: Lepidoptera such as,for example, Adoxophyes spp., Tortrix viridana, Cheimatobia brumata,Lyonetia clerkella, Operophthera brumata, Lithocelletis blancardella,and other boring moths, Laspeyresia spp., Porthetria dispar, Orgyiaspp., Choristoneura spp., Clysia ambiguella, Lobesia botrana, Agrotissegetum, Heliothis spp., Spodoptera spp., Ostrinia nubilalis, Ephestiaspp., Galleria mellonella, Plodia interpunctella.

Homoptera, i.e., shield and soft lice such as, for example, Aspidiotusspp., Saissetia spp., Quadraspidiotus perniciosus, Aonidella aurantii,Coccus spp., Unaspis spp., Lecania spp., as well as Lepidosaphes spp.,Planococcus spp., Pseudococcus spp., Ceroplastes spp., Icerya purchasi,chrysomphalus spp., Parlatoria spp., Rhizoecus spp., as well as cicadasuch as, for example, Nephotettix spp., Laodelphax spp., Nilaparvataspp., as well as leaf suckers such as, for example, Psylla mali, Psyllapiri, Psylla pirisuga, Psylla piricula, Trioza apicalis, aphids such as,for example, Aphis fabae, Myzus persicae, as well as white flies suchas, for example, Trialeurodes vaporariorum, Aleurodes proletella,Bemisia tabaci.

Diptera such as, for example, Aedes aegypti, Culex pipiens, Aedestaeniorrhynchus, Anopheles stephensi, Calliphora spp., Musca domestica,Sciara spp., Phorbia spp., mushroom flies.

Coleoptera such as, for example, Oryzaephilus surinamensis, Rhizoperthadominica, Sitophilus granarius, Sitophilus oryzae, Tenebrio molitor,Tribolium castaneum, Trogoderma granarium, Lasioderma serriorne,Epilachna spp., Leptinotarsa spp., Otiorhynchus sulcatus, Diabroticaspp., and other soil Coleoptera.

Orthoptera such as, for example, Blattella germanica, Leucophaeasurinamensis, Nauphoeta cinerea, Blatta orientalis, Periplanetaamericana.

Heteroptera such as, for example, Dysdercus cingulatus, Rhodniusprolixus, Oncopeltus fasciatus, Piesma spp., Lygus spp.

Isoptera (termite species)

Hymenoptera such as, for example, Solenopsis invicta, Monomoriumpharaonis, Atta spp., as well as true sawflies such as, for example,Athalia rosae, Hoplocampa spp., Pristiphora spp.

Acarina such as, for example, Tetranychus urticae, Tetranychuscinnabarinus, Panonychus ulmi and other Tetranychida, Eriophyida such asPhyllocoptruta oleivora, and, in addition, especially ticks.

Nematoda such as, for example, Ditylenchus dipsaci, Meliodogyneincognita, Pratylenchus penetrans, Aphelenchoides rizemabosi andGlobodera rostochiensis.

The compounds of formula I of this invention act as contact or feedpoisons and are also effective in the vapor phase. In contrast to mostof the hitherto known pest control agents, which act as toxins on thenervous system of the animals and thereby kill, cripple or repel them,the compounds of formula I of this invention interfere with the hormonalsystem of the animal organism. In the case of insects, for example, themetamorphosis to the imago, the laying of viable eggs and thedevelopment of laid normal eggs is disturbed. Moreover, in variousinsect species the larval moultings are disturbed. The sequence ofgenerations is interrupted and the animals are indirectly killed.

The compounds of formula I are practically non-poisonous to vertebratessince the toxicity is above 1000 mg/kg body weight. The compounds offormula I are also readily degraded and the danger of accumulation istherefore extruded. Therefore, they can accordingly be used for thecontrol of pests on animals, plants, provisions and materials and inwater.

The instant invention is also directed to pesticidal compositions suchas solutions, emulsions, suspensions, powders, pastes and granulateswhich contain inert carrier materials and, as the active ingredient, oneor more of the compounds of formula I.

These compositions are prepared by known methods such as, for example,by mixing the active substance with extenders (liquid solvents,liquified gases under pressure and/or solid carrier substances) and, ifdesired, surface-active agents (emulsifiers, wetting agents ordispersing agents). When water is used as the extender, organic solventscan also be used as auxiliary solvents.

Examples of liquid solvents include: aromatics such as xylenes, tolueneand alkylnaphthalenes; chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes and methylenechloride; aliphatic hydrocarbons such as cyclohexane and paraffins(e.g., petroleum fractions); alcohols such as butanol and glycol as wellas their ethers and esters; ketones such as acetone, methyl ethylketone, methyl isobutyl ketone and cyclohexanone; strongly polarsolvents such as dimethylformamide, N-methylpyrrolidone anddimethylsulfoxide, and water.

Examples of liquified gaseous extenders or carrier substances includeliquids which are gaseous at normal temperature and under normalpressure such as aerosol propellants, e.g., halogenated hydrocarbons(e.g., dichlorodifluoromethane).

Examples of solid carrier substances include natural mineral substancessuch as kaolins, clays, talc, chalk, quartz, attapulgite,montmorillonite and diastomaceous earth, and synthetic mineralsubstances such as high-dispersible silicic acid, aluminum oxide andsilicates.

Surface-active agents, especially emulsifying agents and wetting agents,suitable for use in the pesticidal compositions of this invention can benon-ionic or anionic. Examples of non-ionic emulsifiers which can beused include polyoxyethylene-fatty acid esters, polyoxyethylene-fattyalcohol ethers and alkylaryl-polyglycol ethers. Examples of anionicemulsifiers include alkyl sulfonates, alkyl sulfates and arylsulfonates.

Examples of dispersing agents include lignin, sulfite lyes and methylcellulose.

The compositions generally contain between 0.0005 weight percent and 95weight percent of compound or compounds of formula I as activeingredient, preferably between 1 weight percent and 75 weight percent.

The pesticidal compositions of the present invention can be inapplication forms suitable for storage or shipment. In such forms (e.g.,emulsifiable concentrates), the concentration of active ingredients isnormally at the higher end of the above concentration range. These formscan then be diluted with the same or different carrier materials toafford active ingredient concentrations suitable for practical use, andsuch concentrations normally lie at the lower end of the above-notedconcentration range. Emulsifiable concentrates generally contain 5 to 95weight percent, preferably 10 to 75 weight percent, of the compound orcompounds of formula I.

The active ingredients can also be used as such in the compositions orin application forms prepared from these compositions such asready-for-use solutions, emulsions, foams, suspensions, powders, pastes,soluble powders, dusting agents and granulates. They are used in theusual procedures such as sprinkling, spraying, smokescreening, dusting,scattering, drilling-in, vaporizing, pouring, drenching or incrustating.

The concentrations of active ingredient in the ready-for-usepreparations can vary over wide limits. In spray liquors, theconcentration lies between 0.0005 weight percent and 20 weight percent.

The active ingredients can also be used with good effect in theultra-low-volume process (ULV) where it is possible to formulate sprayliquors having preferably from 0.5 to 20 weight percent.

The active ingredients can also be used with good effect in thelow-volume process and in the high-volume process where it is possibleto formulate spray liquors having from 0.02 to 1.0 or 0.002 to 0.1weight percent of active ingredient respectively.

In granulates, which are used especially in mosquito control, theconcentration of active ingredients is preferably from 1 to 10 weightpercent of the compound or compounds of formula I as the activesubstance.

The pesticidal compositions of the present invention can contain otheractive substances, for example, other pesticides, besides the compoundsof formula I. Such combination compositions are suitable for increasingthe activity or for broadening the spectrum of activity.

In preparing the pesticidal compositions of the present invention, theactive ingredient of formula I is mixed with inert carrier material. Inthe case of pulverous compositions, the active ingredient can be mixedwith the carrier substances, for example, by milling together; or theinert carrier material can be impregnated with a solution or suspensionof the active ingredient and then the solvent or suspension agent can beremoved by evaporation, heating or by filtering under reduced pressure.By the addition of wetting and/or dispersing agents such pulverouscompositions can be made readily wettable with water so that they can beconverted into aqueous suspensions which are suitable, for example, asspray compositions. For the manufacture of emulsifiable concentrates,which are especially suitable for storage and shipment, the activeingredient can be mixed, for example, with an emulsifying agent ordissolved in an inert solvent and thereafter mixed with an emulsifier.Ready-for-use emulsions are prepared by diluting such concentrates withwater.

The pesticidal compositions of the present invention are used bytreating the locus to be protected or the pests themselves with acompound of this invention or with the pesticidal compositions of thepresent invention. This method of use is preferably carried out byapplying the composition to the soil or leaves, or by application to theanimals, provisions or materials to be protected, depending on the peststo be controlled. The control is achieved, for example, by contact or byintake with food.

In addition to their pesticidal properties, the compounds of formula Iof this invention exhibit properties which produce an improvement in thequality of the silk thread in sericulture. Therefore, the compounds offormula I can be used in sericulture as additives to the feed ofsilkworms.

The following Examples illustrate the present invention:

I. Preparation of the active substances

EXAMPLE 1

18.6 g of p-phenoxyphenol are dissolved in 100 ml of dimethylformamide.18.2 g of ethyl (2-chloroethyl)-methylcarbamate and 27.6 g of potassiumcarbonate are added thereto and the reaction mixture is heated at 80° C.while stirring for 15 hours. The reaction mixture is poured into 300 mlof water and extracted with diethyl ether. The ether extract is washedwith semi-saturated and saturated sodium chloride solution, dried oversodium sulfate and evaporated. Chromatography on silica gel usingn-hexane/ethyl acetate (9:1) as the eluent yields ethyl[2-(p-phenoxyphenoxy)ethyl]methylcarbamate; n_(D) ²⁰ =1.5503.

Compounds of formula I are prepared from appropriate starting materialsaccording to the procedure described above:

(1) p-(p-fluorophenoxy)phenol and ethyl (2-chloroethyl)methylcarbamateyield ethyl [2-[p-(p-fluorophenoxy)phenoxy]ethyl]methylcarbamate; n_(D)²⁰ =1.5373;

(2) p-benzylphenol and ethyl (2-chloroethyl)methylcarbamate yield ethyl[2-(p-benzylphenoxy)ethyl]methylcarbamate; n_(D) ²⁰ =1.5495;

(3) p-phenoxyphenol and ethyl (2-chloroethyl)ethylcarbamate yield ethyl[2-(p-phenoxyphenoxy)ethyl]ethylcarbamate; n_(D) ²⁰ =1.5446;

(4) p-phenoxyphenol and ethyl (2-chloroethyl)isopropylcarbamate yieldethyl [2-(p-phenoxyphenoxy)ethyl]isopropylcarbamate; n_(D) ²⁰ =1.5415;

(5) p-phenoxyphenol and ethyl (2-chloroethyl)-n-butylcarbamate yieldethyl [2-(p-phenoxyphenoxy)ethyl]-n-butylcarbamate; n_(D) ²⁰ =1.5358;

(6) p-(m-bromophenoxy)phenol and ethyl (2-chloroethyl)methylcarbamateyield ethyl [2-[p-(m-bromophenoxy)phenoxy]ethyl]methylcarbamate; n_(D)²⁰ =1.5672;

(7) p-phenoxyphenol and ethyl 2-(methylsulphonyloxy)propylcarbamateyield ethyl 2-(p-phenoxyphenoxy)propylcarbamate; m.p. 79°-81° C.;

(8) p-(m-bromophenoxy)phenol and ethyl2-(methylsulphonyloxy)propylcarbamate yield ethyl2-[p-(m-bromophenoxy)phenoxy]propylcarbamate; n_(D) ²⁰ =1.5660;

(9) p-(m-fluorophenoxy)phenol and ethyl (2-chloroethyl)methylcarbamateyield ethyl [2-[p-(m-fluorophenoxy)phenoxyl ethyl]methylcarbamate; n_(D)²⁰ =1.5386;

(10) p-(4-chloro-o-tolyloxy)phenol and ethyl(2-chloroethyl)methylcarbamate yield ethyl[2-[p-(p-chloro-o-tolyloxy)phenoxy]ethyl]methylcarbamate; n_(D) ²⁰=1.5537;

(11) p-phenoxy-m-cresol and ethyl (2-chloroethyl)methylcarbamate yieldethyl [2-(p-phenoxy-m-tolyloxy)ethyl]methylcarbamate; n_(D) ²⁰ =1.546;

(12) p-phenoxyphenol and methyl (2-chloroethyl)methylcarbamate yieldmethyl [2-(p-phenoxyphenoxy)ethyl]methylcarbamate; n_(D) ²⁰ =1.5578;

(13) p-phenoxyphenol and isopropyl (2-chloroethyl)methylcarbamate yieldisopropyl [2-(p-phenoxyphenoxy)ethyl]methylcarbamate; n_(D) ²⁰ =1.5388;

(14) p-phenoxyphenol and methyl 2-(methylsulphonyloxy)propylcarbamateyield methyl 2-(p-phenoxyphenoxy)propylcarbamate; n_(D) ²⁰ =1.5565;

(15) p-phenoxyphenol and isopropyl 2-(methylsulphonyloxy)propylcarbamateyield isopropyl 2-(p-phenoxyphenoxy)propylcarbamate; n_(D) ²⁰ =1.5422;

(16) p-(3,5-dichlorophenoxy)phenol and ethyl(2-chloroethyl)methylcarbamate yield ethyl[2-[p-(3,5-dichlorophenoxy)phenoxy]ethyl]methylcarbamate; n_(D) ²⁰=1.5632;

(17) P-(α,α,α-trifluoro-m-tolyloxy)phenol and isopropyl(2-chloroethyl)methylcarbamate yield isopropyl[2-[p-(α,α,α-trifluoro-m-tolyloxy)phenoxy]ethyl]methylcarbamate; n_(D)²⁰ =1.5092;

(18) p-(m-tolyloxy)phenol and ethyl (2-chloroethyl)methylcarbamate yieldethyl [2-[p-(m-tolyloxy)phenoxy]ethyl]methylcarbamate; n_(D) ²⁰ =1.5485;

(19) p-(nitrophenoxy)phenol and ethyl (2-chloroethyl)methylcarbamateyield ethyl [2-[p-(p-nitrophenoxy)phenoxy]ethyl]methylcarbamate; n_(D)²⁰ =1.5773;

(20) 4-hydroxy-benzophenone and isopropyl (2-chloroethyl)methylcarbamateyield isopropyl [2-(p-benzoylphenoxy)ethyl]methylcarbamate; n_(D) ²⁰=1.5608;

(21) p-(p-fluorobenzoyl)phenol and ethyl2-(methylsulphonyloxy)propylcarbamate yield ethyl2-[p-(p-fluorobenzoyl)phenoxy]propylcarbamate; n_(D) ²⁰ =1.5682;

(22) p-(m-bromophenoxy)phenol and isopropyl2-(methylsulphonyloxy)propylcarbamate yield isopropyl[2-[p-(m-bromophenoxy)phenoxy]propylcarbamate; n_(D) ²⁰ =1.5590;

(23) p-phenoxyphenol and S-ethyl (2-chloroethyl)methylthiocarbamateyield S-ethyl [2-(p-phenoxyphenoxy)ethyl]methylthiocarbamate; m.p.28°-32° C.;

(24) p-(m-chlorophenoxy)phenol and ethyl2-(methylsulphonyloxy)propylcarbamate yield ethyl2-[p-(m-chlorophenoxy)phenoxy]propylcarbamate; n_(D) ²⁰ =1.5578;

(25) p-(m-chlorophenoxy)phenol and ethyl (2-chloroethyl)methylcarbamateyield ethyl [2-[p-(m-chlorophenoxy)phenoxy]ethyl]methylcarbamate; n_(D)²⁰ =1.5570;

(26) p-(m-nitrophenoxy)phenol and ethyl2-(methylsulphonyloxy)propylcarbamate yield ethyl2-[p-(m-nitrophenoxy)phenoxy]propylcarbamate; n_(D) ²⁰ =1.5640;

(27) p-(m-nitrophenoxy)phenol and ethyl (2-chloroethyl)methylcarbmateyield ethyl [2-[p-(m-nitrophenoxy)phenoxy]ethyl]methylcarbamate; n_(D)²⁰ =1.5639;

(28) p-(p-fluorophenoxy)phenol and ethyl2-(methylsulphonyloxy)propylcarbamate yield ethyl2-[p-(p-fluorophenoxy)phenoxy]propylcarbamate; m.p. 98°-100° C.;

(29) p-(o-fluorophenoxy)phenol and ethyl (2-chloroethyl)methylcarbamateyield ethyl [2-[p-(o-fluorophenoxy)phenoxy]ethyl]methylcarbamate; n_(D)²⁰ =1.5399;

(30) p-benzylphenol and ethyl 2-(methylsulphonyloxy)propylcarbamateyield ethyl 2-(p-benzylphenoxy)propylcarbamate; n_(D) ²⁰ =1.5538;

(31) 4-hydroxy-benzophenone and ethyl2-(methylsulphonyloxy)propylcarbamate yield ethyl2-(p-benzoylphenoxy)propylcarbamate; n_(D) ²⁰ =1.5820;

(32) 4-hydroxy-benzophenone and ethyl (2-chloroethyl)methylcarbamateyield ethyl [2-(p-benzoylphenoxy)ethyl]methylcarbamate; n_(D) ²⁰=1.5772;

(33) p-(p-chlorobenzyl)phenol and ethyl (2-chloroethyl)methylcarbamateyield ethyl [2-[p-(p-chlorobenzyl)phenoxy]ethyl]methylcarbamate; m.p.56°-58° C.;

(34) p-(m-fluorophenoxy)phenol and ethyl2-(methylsulphonyloxy)propylcarbamate yield ethyl2-[p-(m-fluorophenoxy)phenoxy]propylcarbamate; n_(D) ²⁰ =1.5382.

II. Preparation of the starting materials

EXAMPLE 2

117.2 g of 2-(n-butylamino)-ethanol are placed in 300 ml of methylenechloride. Then 54.3 g of ethyl chloroformate are allowed to drop induring 1 hour at 30°-35° C. with ice-cooling. After stirring for anadditional 2 hours, the methylene chloride is evaporated and the residueis distilled to yield pure ethyl (2-hydroxyethyl)-n-butylcarbamate; b.p.112° C./0.1 Torr.

52 g of ethyl (2-hydroxyethyl)-n-butylcarbamate are placed in 125 ml ofmethylene chloride and treated dropwise with 41.6 g of thionyl chlorideduring 45 minutes at 20°-25° C. Then the mixture is allowed to react foran additional 1 hour at room temperature. After removing the solvent,the residue is distilled to yield pure ethyl(2-chloroethyl)-n-butylcarbamate; b.p. 91° C./0.07 Torr.

In an analogous manner to that described in this Example, the followingcompounds are prepared:

(1) 2-isopropylamino-ethanol and ethyl chloroformate yield ethyl(2-hydroxyethyl)isopropylcarbamate of b.p. 93° C. at 0.07 Torr; andreaction with thionyl chloride yields ethyl(2-chloroethyl)isopropylcarbamate; b.p. 84° C./0.1 Torr;

(2) 2-methylamino-ethanol and methyl chloroformate yield methyl(2-hydroxyethyl)methylcarbamate of b.p. 88°-91° C./0.1 Torr; andreaction with thionyl chloride yields methyl(2-chloroethyl)methylcarbamate; b.p. 86°-90° C./0.15 Torr;

(3) 2-methylamino-ethanol and isopropyl chloroformate yield isopropyl(2-hydroxyethyl)methylcarbamate of b.p. 100° C./0.15 Torr; and reactionwith thionyl chloride yields isopropyl (2-chloroethyl)methylcarbamate;b.p. 72° C./0.15 Torr;

(4) 2-methylamino-ethanol and S-ethyl chlorothioformate yield S-ethyl(2-hydroxyethyl)methylthiocarbamate of b.p. 110°-115° C./0.2 Torr; andreaction with thionyl chloride yields S-ethyl(2-chloroethyl)methylthiocarbamate; b.p. 70°-75° C./0.1 Torr;

(5) 1-amino-2-propanol and isopropyl chloroformate yield isopropyl2-hydroxypropylcarbamate; b.p. 105°-111° C./0.65 Torr.

EXAMPLE 3

32.3 g of hydroquinone are dissolved in 250 ml of dimethyl sulphoxide.With stirring and constant introduction of nitrogen there aresuccessively added 100 ml of toluene and 30 g of 86% potassiumhydroxide. Then the bath temperature is adjusted to 160° C. and thewater is completely removed by means of a water separator. Thereafter,the bath temperature is increased further and the toluene is distilledoff until the internal temperature had attained 155° C. Then 40 g of3-bromo-fluorobenzene are allowed to flow in and the mixture is held for20 hours at this temperature. Thereafter, the dimethyl sulphoxide isdistilled off in a water-jet vacuum. The cooled residue is poured intoice-water, made neutral with hydrochloric acid and extracted three timeswith ethyl acetate. The extracts are washed twice with water and oncewith saturated sodium chloride solution, dried over sodium sulfate andevaporated. Chromatography on silica gel with n-hexane/ethyl acetate(9:1) yields p-(m-bromophenoxy)phenol; n_(D) ²⁰ =1.6018.

In an analogous manner to that described in the preceding paragraph,hydroquinone and 3-trifluoromethyl-chlorobenzene in the presence of acatalytic amount of copper powder yieldp-(α,α,α-trifluoro-m-tolyloxy)-phenol which distils in the bulb-tube at140° C./0.05 Torr; n_(D) ²⁰ =1.5370.

EXAMPLE 4

29.4 g of ethyl 2-hydroxypropylcarbamate are dissolved in 27 g oftriethylamine and 22.9 g of methanesulphonyl chloride are added dropwisethereto at 15°-20° C. over 1 hour while stirring. The thickeningreaction mixture is stirred for 2.5 hours and then poured intoice-water. The mixture is acidified by means of 2 N hydrochloric acidand extracted three times with methylene chloride. The extracts arewashed neutral with water and dried over sodium sulfate. Afterevaporating the solvent, there is obtained ethyl2-(methylsulphonyloxy)propylcarbamate (n_(D) ²⁰ =1.4577) which can beused without further purification.

In an analogous manner to that described above,

(1) methyl 2-hydroxypropylcarbamate and methanesulphonyl chloride yieldmethyl 2-(methylsulphonyloxy)propylcarbamate (m.p. 37°-40° C.) which canbe used without further purification;

(2) isopropyl 2-hydroxypropylcarbamate and methanesulphonyl chlorideyield isopropyl 2-(methylsulphonyloxy)propylcarbamate.

EXAMPLE 5

21.8 g of sodium hydride (55% in oil) are placed in 100 ml of absolutepyridine and treated dropwise during 1 hour with 54.1 g of m-cresol in200 ml of pyridine. After completion of the reaction, 1.2 g of cuprouschloride are added and subsequently 93.5 g of 4bromoanisole are addeddropwise during 1 hour at reflux temperature. After refluxing for 4hours, the pyridine is distilled off, the mixture being heated at theend up to 170° C. (internal temperature). After 2 hours, 350 ml of waterare added dropwise with ice-cooling, followed by 500 ml of diethyl etherand a further 150 ml of water. The mixture is filtered with suction overCelite and the phases are separated. The organic phase is washed insequence with 200 ml of 2 N hydrochloric acid, three times with 100 mlof 2 N sodium hydroxide each time, with 200 ml of water and with 200 mlof saturated sodium chloride solution. After drying over sodium sulfateand evaporation, there is obtained a brown-red oil which is filteredover a five-fold amount of silica gel with n-hexane/diethyl ether andthen distilled to yield pure p-(m-tolyloxy)anisole; b.p. 106°-108°C./0.04 Torr; n_(D) ²⁰ =1.5738.

77 g of p-(m-tolyloxy)anisole are dissolved in 360 ml of acetic acid andtreated with 300 ml of 48% hydrobromic acid. Then, the mixture isallowed to react at reflux temperature for 5 hours. The cooled solutionis poured into 1.5 l of ice-water and extracted three times with 150 mlof methylene chloride each time. The organic solution is washed threetimes with 150 ml of water each time and with 150 ml of saturated sodiumbicarbonate solution, dried over sodium sulfate and evaporated.Distillation of the crude product yields pure p-(m-tolyloxy)phenol; b.p.88°-89° C./0.04 Torr.

In an analogous manner to that described above in this Example,

(1) 4-chloro-o-cresol and 4-bromoanisole yieldp-(p-chloro-o-tolyloxy)anisole of b.p. 112°-116° C./0.04 Torr andreaction with hydrobromic acid/acetic acid yieldsp-(p-chloro-o-tolyloxy)phenol; m.p. 83°-85° C.;

(2) m-nitrophenol and bromoanisole yield p-(m-nitrophenoxy)anisole ofm.p. 69°-71° C. and reaction with hydrobromic acid/acetic acid yieldsp-(m-nitrophenoxy)phenol which distils in the bulb-tube at 95°-97°C./0.04 Torr;

(3) 4-methoxy-o-cresol and bromobenzene yield 5-methoxy-2-phenoxytolueneof b.p. 102°-104° C./0.035 Torr and m.p. 39°-42° C. and reaction withhydrobromic acid/acetic acid yields p-phenoxy-m-cresol; m.p. 96°-99° C.;

(4) m-fluorophenol and 4-bromoanisole yield p-M-fluorophenoxy)anisole ofb.p. 130°-131° C./0.2 Torr and reaction with hydrobromic acid/aceticacid yields p-(m-fluorophenoxy)phenol; m.p. 53°-55° C.

III. Formulation Examples

EXAMPLE 6

An emulsifiable concentrate appropriate for liquid compounds of formulaI can contain the following ingredients:

    ______________________________________                                                                g/l                                                   ______________________________________                                        Active ingredient, a compound of formula I                                                              250                                                 N--Methyl-2-pyrrolidone   300                                                 Alkylphenol-ethylene oxide adduct                                                                       35                                                  Calcium salt of dodecylbenzene-sulphonic acid                                                           15                                                  Cycloalkylepoxystearate   25                                                  Aromatic solvent (mixture of C.sub.10 --alkylbenzenes)                                                  ad 1000 ml                                          ______________________________________                                    

The active ingredient is dissolved in the N-methyl-2-pyrrolidone,thereafter the remaining ingredients are added and dissolved, and themixture is made up to volume with the aromatic solvent. To prepare aready-for-use spray liquor the present product is added to water, tospontaneously yield an emulsion (o/w) which is stable for hours.

EXAMPLE 7

A spray powder appropriate for all compounds of formula I can containthe following ingredients:

    ______________________________________                                                               Wt. %                                                  ______________________________________                                        Active ingredient, a compound of formula I                                                             25                                                   Silicic acid, hydrated (about 87% SiO.sub.2)                                                           30                                                   Sodium lauryl sulphate   2                                                    Sodium lignosulphonate   4                                                    Kaolin, mainly Al.sub.2 [Si.sub.2 O.sub.5 ](OH).sub.4                                                  39                                                                            100                                                  ______________________________________                                    

The active ingredient is homogeneously mixed with the remainingcomponents in a suitable apparatus. The resulting powder is finelyground in a suitable grinding apparatus (e.g. pinned disc mill, hammermill, ball mill or air-jet mill) to a particle size necessary for anoptimum biological activity and therafter again mixed. The present spraypowder is spontaneously wetted by water and gives well-suspendible,ready-for-use spray liquors.

EXAMPLE 8

A granulate appropriate for all compounds of formula I can contain thefollowing ingredients:

    ______________________________________                                                                  Wt. %                                               ______________________________________                                        Active ingredient, a compound of formula I                                                                5                                                 Tetrasodium salt of ethylenediaminotetraacetic acid                           (Na.sub.4 --EDTA)           1                                                 Pumice stone granulate 0.6-1.0 mm                                                                         94                                                                            100                                               ______________________________________                                    

The pumice stone granulate is placed in a suitable mixing mill and anaqueous solution of the Na₄ -EDTA is sprayed on with constant stirring.The mixture is dried at 110° C. and thereafter the active ingredient,dissolved in a suitable solvent (e.g. methylene chloride), is sprayed onthe dry mixture. The solvent is evaporated by warming. There results awell-shakeable granulate which can be applied to the soil or to water byhand, with suitable granulate spreaders or even from aircraft. Theporous structure of the pumice stone brings about in many cases adesirable delayed release of the active ingredient over a long time.

I claim:
 1. Ethyl [2-(p-phenoxyphenoxy)ethyl]methylcarbamate. 2.S-ethyl[2-(p-phenoxyphenoxy)ethyl]methylthiocarbamate.
 3. A pesticidalcomposition which comprises an inert carrier material and, as the activeingredient, an amount which is effective as a pesticide of a compoundaccording to claim
 1. 4. A pesticidal composition which comprises aninert carrier material and, as the active ingredient, an amount which iseffective as a pesticide of a compound according to claim
 2. 5. A methodfor the control of pests, which comprises applying to the site to betreated or the pests themselves, an amount of the compound according toclaim 1 which is effective in the control of pests.
 6. A method for thecontrol pests, which comprises applying to the site to be treated or thepests themselves, an amount of the compound according to claim 2 whichis effective in the control of pests.